Paint fungicide

ABSTRACT

Dialkyl 1,1&#39;&#39;-(hydrocarbylenebiscarbamoyl)bis(2benzimidazolecarbamates) are useful as paint fungicides.

United Sta1 Dittmar PAINT FUNGICIDE Bruce Ivor Dittmar, Wilmington, Del.

Inventor:

E. I. Du Pont de Nemours and Company, Wilmington, Del,

Filed: Dec. 17, 1973 App]. No.: 425,070

Related US. Application Data Division of Ser. No. 229,559, Feb. 29, 1972, which is a continuation-in-part of Ser. No. 841,987, July 15, 1969, abandoned.

Assignee:

US. Cl. 260/29.6 MN; 106/15 AF; 117/161 R; 260/17 R; 260/4255; 260/3092 [4 1 Sept. 16, 1975 Int. Cl. C09D 5/14 Field of Search 260/296 MN, 309.2; 106/15 AF; 424/273 [56] References Cited UNITED STATES PATENTS 3,817,760 6/1974 Brake 106/15 AF Primary Examiner-Lucille M. Phynes ABSTRACT I ,1 -(hydrocarbylenebiscarbamoyl )bis( 2- Dialkyl benzimidazolecarbamates) are useful as paint fungicides.

4 Claims, No Drawings PAINT EUNGICIDE moyl )-bis-2-benzimidazolecarbamatesJ and their use as fungicides for paints.

SUMMARY OF THE INVENTION It has been found that outstanding fungicidal activity can be obtained by incorporating into paint the following compounds: dimethyl phenylenedicarbamoyl)bis( 2 benzimidazolecarbamate O O !'OCH g-OCH; {m L H Belgian Pat. No.

dimethyl l,l '-(p-phenylenedicarbamoyl )bis( 2- benzimidazolecarbamatei), 1 1

dimethyl U y ,1, l[n 1ethylenedi-(pphenylcarbamoyl bi's( 2'-hnzirnidagolecarbamate) dimethyl cyclohexylcarbamoyl )]bis (2 benzimidazolecarbamate I I I The preferred compound for use is dimethyl 1,1 -(4- methyl-m-phenyleiiedicarbamoyl )bis( 2- and l,l '[rnethylenedi-( 4- benzimidazolecarbamate PREPARATION- PROCEDURES The compounds of this ihventi on can be prepared by reacting 2 moles of methyl 2-benzimi'dazolecarbamate (I) with an optionally substituted hydrocar byl'ene diisowhere A is methylenedi-p-phenylene),p-phenylene, 4-methyl-mphenylene, or methylenedi-(4-cyclohexyl).

The starting methyl Z-benzimidazolecarbamates (1) can be prepared by methods known to the art, c.g., by a three-reaction sequence taught in U.S. Pat. No.

Hydrocarbylene diisocyanatesmay be prepared by reacting the corresponding diamine with phosgene [Siefl en, Ann., 562, 76 (1948)].

The following examples serve to illustrate the general method of preparation of the compounds of-this invention. Unless otherwise stated, all parts are by weight.

EXAMPLE 1 Preparation of Dimethyl l,1-(4-methyl-mphenylenedicarbamoyl )bis( 2- benzimidazolecarbam ate) To a stirred mixture of methyl 2 benzimidazolecarbamate (19.1 parts) and triethylamine (0.1 part) in methyl ethyl ketone (300 parts) was slowly added 4-methyl-m-phenylene diisocyanate (8.7 parts) in methyl'ethyl ketone parts). The reaction mixture was stirred at room temperature for one hour, filtered to recover the solid phase. The solid was air dried overnight. The product dimethyl 1,1 '-(4-methylm-phenylenedicarbamoyl )-bis( 2- benzimidazolecarbamate) (27.3 parts) exhibited a melting point of 203-205C.

EXAMPLE 2 Preparation of Dimethyl 1,1-(p-phenylenedicarbamoyl)bis-(2- benzimidazolecarbamate) To a stirred mixture of methyl 2- benzimidazolecarbamate (19.1 parts) and triethylamine (0.1 part) in methyl ethyl ketone (300 parts) was slowly added p-phenylene diisocyanate (8 parts) in methyl ether ketone (20 parts). The reaction mixture was stirred at room temperature overnight. The solid was recovered from the reaction mixture by filtration and air dried. The product dimethyl 1,1 '-(p phenylenedicarbamoyl)bis(2- benzimidazolecarbamate) (26 parts) exhibited a melting point of 350C.

EXAMPLE 3 Preparation of Dimethyl 1,1 -[methylenedi-(p-phenylcarbamoyl )]bis( 2- benzimidazolecarbamate) .1'-[methylenebis(4- As mentioned previously. it has been found that the compounds of Formula I possess outstanding fungicidal activity when employed to prevent or mitigate damage to paint and painted surfaces. Painted surfaces are protected from stain and discoloration caused by mildew by incorporation ofa compound of this invention in the paint formulation.

Painted surfaces can be so protected by incorporating in the paint formulation, prior to application, 5 to 20,000 parts per million of an active compound of this invention. More preferred rates are in the range of 10 to 10,000 parts per million and the most preferred rates are in the range of 20 to 5,000 parts per million. Such treatments with the compounds of this invention also protect the paint while still in the can from deterioration by fungi.

The active compounds are dispersed in the paint formulation by any of the conventional techniques such as dispersing the compound in the liquid vehicle used for the paint and adding the film former.

Further details on the activity and formulation of the active ingredients can be found in the parent application, i.e., Ser. No. 229,559, filed Feb. 29, 1972.

EXAMPLE 4 A latex house paint formulation contains the following ingredients:

carbamoyl )bis( Z-bcnzimidazolccarbamate) The above materials are ground in a high-speed mill and let down, at a slower speed, as follows:

Parts Acrylic resin:

Rhoplex*A('388 (507:) 459.8 Antifoamer:

Nopco NDW l Ammonium hydroxide (287:) 2 Tributyl phosphate Premix 1 1.5 Propylene glycol 35 Water and/or hydroxycthyl cellulose (2.5%) 17.5 Toner: Cal/Ink GP88|4E Phthalo Blue 0.05

Cal/Ink (iPX807B Lamp Black *'l'rade name of Rohm tv Haas ('ompan Philadelphia. Pa. for aqueous dispersion of acrylic cupol ruci'sv Two coats of the latex paint was applied to Whatman No. 1 filter paper substrate. The first coat was allowed to dry for 24 hours before the second was applied. A 1 V2 inch square of the coated paper was subjected to heat (C) for 24 hours followed by running tap water for 24 hours. The resulting paint chip is placed on the surface of malt agar in a petri plate and inoculated with an aqueous suspension of PuIIu/uriu pullulunx (the predominant fungus isolated from mildew on painted surface). After a period of 4 weeks, the paint chip had of fungi:

Dimethyl 1,1 -(p-phenylenedicarbamoyl)bis(2- benzimidazolecarbamate) Dimethyl 1,1 '-[methylenedi-(pphenylcarbamoyl bis( Z-benzimidazolecarbamate) Dimethyl 1,1 -[methylenebis(4- cyclohexylcarbamoyl ]bis( 2- benzimidazolecarbamate) EXAMPLE 5 Example 4 is repeated using 012 part of the fungicide in place of the 1.2 parts. Paint chips prepared from the resulting formulation give similar results in inhibiting the growth of Pullularia pullulans.

EXAMPLE 6 Example 4 is repeated using 6 parts of the fungicide in place of the 1.2 parts. Paint chips prepared from the resulting formulation give similar results in inhibiting the growth of Pulluluriu pullulans.

I claim:

1. A fungus-resistant paint composition comprising a dispersion of a film-former in a liquid vehicle containing 5 to 20,000 parts per million by weight, basis total paint composition, of a fungicidal compound selected from the group consisting of dimethyl phenylenedicarbamoyl)bis(2- benzimidazolecarbamate); dimethyl 1,1 '-(p-phenylenedicarbamoyl)bis( 2- benzim'idazolecarbamate dimethyl phenylcarbarhoyl)]bis(2- benzimidazolecarbamate); and

dimethyl 1,1 '-[methylenedi-(4- cyclohexylcarbamoyl ]-bis( 2 benzimidazolecarbamate 2. The paint composition of claim 1 in which the dispersion of film-former is a latex.

3. The paint composition of claim 1 containing I0 to 10,000 parts per million by weight of fungicidal compound.

4. The paint composition of claim 3 in which the fungicidal compound is dimethyl 1,] -(4-methyl-mphenylenedicarbamoyl )bis( 2- benzimidazolecarbamate 1,1 '-[methylenedi-(p- 

1. A FUNGOS-RESISTANT PAINT COMPOSITION COMPRISING A DISPERSION OF A FILM-FORMER IN A LIQUID VEHICLE CONTAINING 5 TO 20,000 PARTS PER MILLION BY WEIGHT, BASIS TOTAL PAINT COMPOSITION, OF A FUNGICIDAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF DIMETHYL 1,1'' -(4-METHYL-M-PHENYLENEDICARBONOYL)BIS(2-BENZIMIDAZOLECARBAMATE), DIMETHYL1,1''-(P-PHENYLENEDICARBOMAYOL)BIST(2ZIMIDAZOLECARBAMATE), DIMETHYL 1,1''-(METHYLENEDI-(P-PHENYLCARBAMOYL))BIS(2BENZIMIDAZOLECARBAMATE), AND DIMETHYL 1,1''-(METHYLENEDI-(4-CYCLOHEXYLCARBAMOYL))BIST(2-BENZIMIDAZOLECARBAMATE).
 2. THE PAINT COMPOSITION OF CLAIM 1 IN WHICH THE DISPERSION OF FILM-FORMER IS A LATEX.
 3. The paint composition of claim 1 containing 10 to 10,000 parts per million by weight of fungicidal compound.
 4. The paint composition of claim 3 in which the fungicidal compound is dimethyl 1,1''-(4-methyl-m-phenylenedicarbamoyl)bis(2-benzimidazolecarbamate). 